Sulfonated polyphenylene (phenylene) ether random copolymer, preparation method and application thereof

Abstract

The present invention discloses sulfonated polyphenylene (phenylene) ether random copolymer, preparation method and application thereof, which has a general chemical formula: wherein, X is 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is 2 to 5 arylene groups or nitrogen-containing heteroarylene groups, C(CF 3 )Ph, C(Ph) 2 ; Z is direct bond, S, C(CF 3 ) 2 , C 3 H 6 , SO 2 , CO 2 , C(CF 3 )Ph, C(Ph) 2 , 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; R 1 is 0 or more of halogen, NO 2 , CN, CF 3 , CH 3 or SO 3 H; R 2 is 1 to 8 aryl groups or nitrogen-containing heteroaryl groups optionally substituted with 0 to 8 substituents of halogen, NO 2 , CN, CF 3 , CH 3 or SO 3 H; R 3 is 0 to 4 substituents of halogen, NO 2 , CN, CF 3 , CH 3 , SO 3 H, aryl or nitrogen-containing heteroaryl; R 4 is 0 or more of halogen, CH 3 , NO 2 , CN or CF 3 , and R 5 is 0 or more of halogen, CH 3 , NO 2 , CN or CF 3 , or 0 to 8 aryl or nitrogen-containing heteroaryl substituted with 0 to 8 substituents of halogen, CH 3 , NO 2 , CN or CF 3 . Whereby, the polyphenyl polymer has hydrophilic part and dense sulfonic acid side chains, membrane made by the polymer with polyphenyl structure does have strong mechanical properties and maintains good dimensional stability when in contact with water for a long time. Through controlling the polymerization equivalent ratio of Z, the ratio between the hydrophilic and hydrophobic segments can be precisely adjusted.

What is claimed is: 
     
         1 . A sulfonated polyphenylene (phenylene) ether random copolymer having a general chemical structure of the following formula: 
       
         
           
           
               
               
           
         
         wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF 3 )Ph groups or C(Ph) 2  groups; R 1  represents 0 or an integer number greater than 0 of halogen, NO 2 , CN, CF 3 , CH 3  or SO 3 H; R 2  represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3 , CH 3  and SO 3 H; R 3  is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO 2 , CN, CF 3 , CH 3 , SO 3 H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF 3 ) 2 , C 3 H 6 , SO 2 , CO 2 , C(CF 3 )Ph, C(Ph 2 ), 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF 3 ) 2 , C 3 H 6 , SO 2 , CO 2 , C(CF 3 )Ph or C(Ph) 2 , R 4  is 0 or an integer number greater than 0 of halogen, CH 3 , NO 2 , CN or CF 3 , and R 5  is 0 or an integer number greater than 0 of halogen, CH 3 , NO 2 , CN or CF 3 ; wherein, when Z is 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R 4  is 1 or an integer number greater than 1 of halogen, CH 3 , NO 2 , CN or CF 3 , and R 5  is 0 to 8 aryl groups or nitrogen-containing heteroarylene groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH 3 , NO 2 , CN and CF 3 ; the repeating unit with the repeating number of n greater than 0 in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment. 
       
     
     
         2 . The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 1 , wherein R 1  and R 4  further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R 2 , R 3  and R 5  are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups. 
     
     
         3 . The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 2 , wherein the aromatic groups of R 1 , R 2  and R 3  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3 , CH 3  and SO 3 H; wherein the aromatic groups of R 4  and R 5  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3  and CH 3 . 
     
     
         4 . The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 1 , wherein through a nucleophilic polycondensation reaction, X, Y and Z are formed by polyphenyl ring monomers x, y and z correspondingly; wherein, when x is a dihalogen or diol monomer having an equivalent ratio of 1, y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when y is a dihalogen or diol monomer having an equivalent ratio of 1, x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1; the equivalent ratios of x, y and z are respectively not equal to 0. 
     
     
         5 . The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 4 , wherein a weight ratio between the hydrophilic and hydrophobic segments is adjustable by controlling the equivalent ratio of z. 
     
     
         6 . A method for preparing the sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 1  comprised the steps of:
 treating three polyphenyl ring monomers x, y and z by a nucleophilic polycondensation reaction to obtain polyphenyl ring segments of X, Y and Z correspondingly; wherein, when the polyphenyl ring monomer x is a dihalogen or diol monomer having an equivalent ratio of 1, the polyphenyl ring monomers y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when the polyphenyl ring monomer y is a dihalogen or diol monomer having an equivalent ratio of 1, the polyphenyl ring monomers x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1, and 
 then through a post-sulfonation reaction to obtain the sulfonated polyphenylene (phenylene) ether random copolymer having a general chemical structure of the following formula: 
 
       
         
           
           
               
               
           
         
         wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF 3 )Ph groups or C(Ph) 2  groups; R 1  represents 0 or an integer number greater than 0 of halogen, NO 2 , CN, CF 3 , CH 3  or SO 3 H; R 2  represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3 , CH 3  and SO 3 H; R 3  is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO 2 , CN, CF 3 , CH 3 , SO 3 H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF 3 ) 2 , C 3 H 6 , SO 2 , CO 2 , C(CF 3 )Ph, C(Ph 2 ), or a third linker group optionally substituted with 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF 3 ) 2 , C 3 H 6 , SO 2 , CO 2 , C(CF 3 )Ph or C(Ph) 2 , R 4  is 0 or an integer number greater than 0 of halogen, CH 3 , NO 2 , CN or CF 3 , and R 5  is 0 or an integer number greater than 0 of halogen, CH 3 , NO 2 , CN or CF 3 ; wherein, when Z is the third linker group of 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R 4  is 1 or an integer number greater than 1 of halogen, CH 3 , NO 2 , CN or CF 3 , and R 5  is 0 to 8 aryl groups or nitrogen-containing heteroarylene groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH 3 , NO 2 , CN and CF 3 ; the repeating unit with the repeating number of n greater than 0 in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment. 
       
     
     
         7 . The method as claimed in  claim 6 , wherein R 1  and R 4  further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R 2 , R 3  and R 5  are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups. 
     
     
         8 . The method as claimed in  claim 7 , wherein the aromatic groups of R 1 , R 2  and R 3  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3 , CH 3  and SO 3 H; wherein the aromatic groups of R 4  and R 5  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3  and CH 3 . 
     
     
         9 . The method as claimed in  claim 6 , wherein the polyphenyl ring segments of X, Y, and Z are randomly copolymerized through the nucleophilic polycondensation reaction to control the post-sulfonation reaction so that the polyphenyl ring segments X and Y are sulfonated to form the hydrophilic segment, the substituents of R 4  and R 5  on the polyphenyl ring segment Z cannot be sulfonated so as to form the hydrophobic segment; wherein, by controlling the equivalent ratio of the polyphenyl ring monomer z, an weight ratio between the hydrophilic and hydrophobic segments is adjusted. 
     
     
         10 . The method as claimed in  claim 6 , wherein a weight ratio between the hydrophilic and hydrophobic segments is adjustable by controlling the equivalent ratio of the polyphenyl ring monomer z; and the equivalent ratios of x, y and z are respectively not equal to 0. 
     
     
         11 . A product made by the sulfonated polyphenylene (phenylene) ether random copolymer as claimed in  claim 1 , the product is formed by the sulfonated polyphenylene (phenylene) ether random copolymer to be proton exchange membranes, coating solutions or electrodes to be applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes. 
     
     
         12 . The product as claimed in  claim 11 , wherein, in the general chemical structure of the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, wherein R 1  and R 4  further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R 2 , R 3  and R 5  are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups. 
     
     
         13 . The product as claimed in  claim 12 , wherein the aromatic groups of R 1 , R 2  and R 3  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3 , CH 3  and SO 3 H; wherein the aromatic groups of R 4  and R 5  respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO 2 , CN, CF 3  and CH 3 . 
     
     
         14 . The product as claimed in  claim 11 , wherein, in the general chemical structure of the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, through a nucleophilic polycondensation reaction, X, Y and Z are formed by polyphenyl ring monomers x, y and z correspondingly; wherein, when x is a dihalogen or diol monomer having an equivalent ratio of 1, y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when y is a dihalogen or diol monomer having an equivalent ratio of 1, x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1; the equivalent ratios of x, y and z are respectively not equal to 0. 
     
     
         15 . The product as claimed in  claim 14 , wherein a weight ratio between the hydrophilic and hydrophobic segments of the sulfonated polyphenylene (phenylene) ether random copolymer is adjustable by controlling the equivalent ratio of the polyphenyl ring monomer z.